Stereoselective benzylic hydroxylation of 2-substituted indanes using toluene dioxygenase as biocatalyst

被引:36
作者
Bowers, NI
Boyd, DR [1 ]
Sharma, ND
Goodrich, PA
Groocock, MR
Blacker, AJ
Goode, P
Dalton, H
机构
[1] Queens Univ Belfast, Sch Chem, Belfast BT9 5AG, Antrim, North Ireland
[2] Zeneca PTD, Huddersfield HD2 1FF, W Yorkshire, England
[3] Univ Warwick, Dept Biol Sci, Coventry CV4 7AL, W Midlands, England
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1999年 / 11期
关键词
D O I
10.1039/a901453e
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Indane, 1A, and a series of 2-substituted indane substrates, 1B-1D, 1G, 1I-1L, were found to undergo benzylic monohydroxylation catalysed by toluene dioxygenase, present in the intact cells of Pseudomonas putida UV 4, to yield enantiopure cis-indan-1-ols, 2A-2D, 2G, 2I-2L of the same absolute configuration at C-1 as major bioproducts. Enantiopure trans-indan-1-ols 6B, 6C, and 6G were also obtained as minor metabolites. Evidence of further sequential benzylic hydroxylation (bis-hydroxylation) was found only with substrates 2A, 1C, 1D and 1L to yield the corresponding enantiopure trans-1,3-diols, 3A, 3C, 3D and 3L. Minor enzyme-catalysed processes also observed include benzylic alcohol oxidation to ketones (4A, 5A, 4B, 4L, 5L), ketone reduction to benzylic alcohol 6A, ester hydrolysis to indan-2-ol 1B, and cis-dihydroxylation of indan-1-ol 6A to triol 7. The enantiopurities and absolute configurations of bioproducts have been determined using MTPA ester formation, circular dichroism spectroscopy and stereochemical correlation methods. The contribution of asymmetric oxidation and kinetic resolution to the production of bioproducts of high ee (>98%), and the metabolic sequence involved in their biotransformation by P. putida UV4 is discussed. Enantiocomplementarity was found during the benzylic hydroxylation of indan-2-ol 1B, using toluene dioxygenase and naphthalene dioxygenase, when both single enantiomers of the metabolites 2B, 4B and 6B of opposite configurations were obtained.
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收藏
页码:1453 / 1461
页数:9
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